Organic products containing pigment dyestuffs



United States Patent 3,132,035 ORGANIC PRODUCTS CONTAINING PIGMENT DYESTUFFS Ernst Reich, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland N0 Drawing. Filed July 19,1960, Ser. No. 43,739 Claims priority, application Switzerland July 27, 1959 8 Claims. (Cl. 106-148) dyed viscose stockings, so that it has been necessary heretofore to employ inorganic brownpigments, more particularly iron oxides. These, however, have the drawback of low color intensity and, owing to their relatively high specific gravity, have a tendency towards sedimentation during the application processes.

It has now been found that compounds of the general formula NO: 6R 6R 1 102 in which R signifies a lower alkyl group, for example an ethyl, propyl, isopropyl, butyl or isobutyl group, and in- 3,132,035, Patented May 5., 1964 ice process, which are obtained as a rule in a physically usable form during synthesis, are advantageously brought into a finely divided state before application, for example by grinding the crude pigments in dry or watery-moist form with or without the addition of an organic solvent and/ or of a salt which can be Washed out.

The pigments to be employed according to the present process may be used either in pure form as so-called toners or in the form of preparations in which the pigment is present in a finely divided state, advantageously with a particle diameter of not more than 3n. Such preparations, which may also contain the usual additions, for example dispersing agents or binders, can be prepared in manner known per se by intensive mechanical treatment, for instance on roll mills or in suitable kneading apparatus. In this connection, the dispersing medium permitting the intensive working up is selected according to the purpose in view, for example to produce aqueous dispersible preparations sulfite waste liquor or dinaphthylmethanedisulfonic acid salts will be employed, and, for the production of acetate silk spinning preparations, acetyl cellulose mixed with a little solvent.

Owing to the favorable physical form in which the products according to the present invention are generally obtained and owing to their chemical inertness and good temperature stability, they can normally be distributed readily in substances or preparations of said kind, this being done advantageously at a time when said substances or preparations do not yet have their final form. The steps required for shaping, such as spinning, moulding, hardening, casting, cementing and the like, can then particular a methyl group, meet to a high degree, as re- J process may be obtained suitably in known manner by condensation of one mol of a 4:4'-diamino 3 :3'-dialkoxydiphenyl with 2 mols of 2:4-dinitrochlorobenzene.

As materials which can be dyed by the present process there may be mentioned, for example, plastic substances, such as rubber, casein, polymerization resins, such as polyvinyl chloride and its co-polymers, polyvinyl acetals, polyethylene, polypropylene, polystyrene and mixed polymers of the latter with polyesters obtained from unsaturated dicarboxylicacids and diols, polyacrylates and their co-polymers, silicone and silicone resins. The pigments to be employedaccording'to the present method are moreover suitable for producing colored condensation resins, in particular aminoplasts, for example urea formaldehyde or melamine formaldehyde resins, polyaddition resins, such as epoxy or polyurethane resins or alkyd resins, and also for manufacturing colored lacquers containing one or thereof said resins in an organic solvent,

, or aqueous emulsions containing one-or more of said resins'or precondensates, if required in the presence'of organic solvents, for example an oil-in-water or a waterin-oil emulsion. Such emulsions are suitable'especially for. impregnating or printing on textiles or other sheet-like structures, such as paper, leather or fabrics consisting of glass fibers, if necessary with subsequent hardening by heat treatment. The pigments to be employed according to the present process may also be employed for producing spin-dyed fibers, for example of viscose, cellulose esters or polyacrylonitrile. Moreover, they can be used with advantage in the manufacture of cosmetic preparations.

The pigments to be employed according to the, present also be carried out readily in the presence of the present pigments without any possible chemical reactions of the substrate, such as further polymerisations, condensations or polyadditions, being impeded. This was not to be expected to begin with, especially the fact that the four nitro groups present in the dyestulf molecule are resistant to the chemicals having a reducing action which are necessary for desulfurizing the viscose.

The following examples illustrate the invention, the parts signifying, unless otherwise stated, parts by weight, the percentages being by Weight, while the temperatures are given in degrees centigrade.

. Example 1 5 parts of the dyestuff of the formula l I l 1 N02 H 00 OOH N02 are mixed with 95 parts of dioctyl phthalate and ground in a ball mill until the dyestulf particles aresmaller than 3n.

0.8 part of this dioctyl phthalate paste is mixed with 13 parts of polyvinyl chloride, 7 parts of titanium dioxide and thereupon rolled out for 5 minutes on a two-roll mill at 140 C.

A brown coloring of good light and migration fastness V is obtained.

The dyestuff. of the Formula I can be obtained as follows:

In a round flask provided with a stirrer, cooler and thermometer, 244 parts of 3 :3dimethoxy-4:4-diaminodiphenyl, 42.5 parts of 2:4-d-ir'1itroa1-chlorobenzene and 20 parts of anhydrous sodium acetate are heated to to C. in 200 par-ts by volume of nitrobenzene while stirring vigorously and the mixtureis kept at this temperature for 7 hours. After cooling to room temperature, the brown reaction product is filtered off and washed on a suction filter with nitrobenzene, chlorobenzene and finale ning process.

. 3 1y alcohol. The filter cake is now worked up into a suspension in 1,000 parts of water and 15 parts of hydro chloric acid of 30% strength, stirred for 30' minutes at 70 to 80 C., and Well filtered by suction. The suction filtration residue is the-reuponvtreated, likewise for 30 minutes at 70 to 80 C., in 1,000 parts of water and 20 parts of caustic soda solution of 30% strength. After filtering, the pigment is washed with water until the filtrate running ofi has a neutral reaction and then dried in vacuo at 80 to 90 C. 48 parts of 4:4-'bis-(2.":4"-diint-rophenylamino) -3 :3'-dimethoxydiphenyl are obtained as a brown powder which, after recrystallization from dimethyl torm'amide, shows the following analysis values.

Calculated: Percent C 54.17

Found: 7

C 54.15 H 3.6-7 N 14.42

Example 2 40 parts of a nitrocellulose acquer, 2.375 parts of titanium dioxide and 0125 part of the dyestuff according to Example 1 are ground for 16 hours in a rod mill. The lacquer obtained is spread out in a thin layer on an aluminium cfoil. A coat of brown lacquer of very good fastness properties is obtained.

Example 3 A mixture consisting of 25 parts of the dyestuff according to Example 1, 2.5 parts of acetyl cellulose (54.5% combined acetic acid), =1 parts of sodium chloride and 50 parts of diacetone alcohol are treated in a kneader while being cooled until the desired degree of fineness of the pigment is attained. 25 parts of Water are then added and keading is carried out until a fine-grained mass has been produced. This is placed on a suction filter and the sodium chloride and the diacetone alcohol are washed out completely with water. The product is dnied in a vacuum cupboard at 85 C. and ground in a hammer mill.

1.33 pants of the pigment preparation obtained are added to an acetate silk spinning mass consisting ot=100 parts of acetyl cellulose and 376 parts of acetone. carried out for 3 hours, this being sufficient for the complete distribution of the dyestufi. The filament obtained from this mass by the usual method afiter the drying process exhibits a brown coloration which has very good fastness properties.

Example 4 0.25 part of the dyestuif according to Example 1 is ground for 24 hours in a rod mill with40 parts of an alkydmelamine stoving lacqucrcontaining 50% of solids and 4.75 par-ts of titanium dioxide. The lacquer obtained is painted in a thin layer on an aluminum foil and baked for one hour at 120 C. "A coat of brown lacquer having good light fastness is obtained.

Example 5 I 4.8 parts of the dyestuif according to Example 1 are ground with 4.8 parts of the sodium salt of 1: 1'-dinaphthylmethane-2:2-disulionic acid and 22.1 parts of water in one of the known colloid mills until all the dyestuff parti- Stirring is cles are smaller than i The pigment suspension ob- H5020 OCBHE The color pigment employed in'pai'agraph 1 may be obtained in the manner described in Example 1 by replacing the 24.4 parts of 3:3-dimethoxy-4:4'-diaminophenyl by 27.2 parts of 3:3'-diethoxy-4:4diam-inodiphenyl. 50 parts of 4:4'=bis-(2":4" dinitrophenylamino)-3:3'-diethoxydiphenyl are obtained which, after recrystallization from 'y-butyrolactone, shows the following analysis values.

Calculated: Percent C 55.63 H 4.00

Found:

Example 6 A dyebath is prepared containing, to 1,000 parts of Water, 15 parts of a mixed-polymer late-x consisting oi 85.8 parts of isobutyl acrylate, 9.6 parts ot acrylonitrile and 4.6 parts of acrylic acid, 15 parts of a 70 emulsion of a methylol melamine allyl ether emulsified with Turkey red oil and modified with soybean tatty acid, 5 0' parts of a Water-soluble methyl ether of a urea formaldehyde condensation product containing, condensed in, more than 2 mols of formaldehyde per mol of urea, 5 parts of the pigment suspension obtained according to Example 5, paragraph 1, and 20 parts of formic acid of 10% strength.

' Cotton fabric is introduced dry at room temperature into the above dyebath, squeezed out on a padder with a liquid absorption of 65 dried normally, if necessary 100 parts of the pigment dyestuff employed in Exam- 7 ple 1 are mixed withf40 parts of the addition product of 15 mols of ethylene oxide and 1 mol of di-tert. butylpara-cresol and 20 parts of water in a kneading apparatus to form a viscous, homogeneous paste and thoroughly kneaded until the dyestufi agglomerates produced during drying have been dispersed uniformly finely. The mass is carefully diluted with parts of water under constant further kneading and finally homogenised by means of a funnel mill or another suitable apparatus until a pliable homogeneous paste is produced which contains practically exclusively dispersed primary dyestuif particles having a diameter of 3p. at the most. 250 parts of a brownpaste containing 40% of pigment are obtained. 60 parts-of this paste are mixed with 850 parts of an oil-in-water emulsion containing 55% of petroleum hydrocarbons, 5% of a styrene-butadiene emulsion mixed polymer and 3.5% of a solution consisting of about 75% by weight of water-insoluble melamine formaldehyde primary condensate modified with n-butanol and about 25% by'weight of n-butanol as separate inner phase and 36.5% of an aqueous solution containing 7.5 parts by weight of an ion-free emulsifier prepared according to patent application Serial No. 603,164 (now US. Patent No. 2,946,767), filed August 9, 1956, by Hans U. Gassmann, Example 3, to 92.5 parts by weight of water as outer phase, 80 parts of water and 10 parts of ammonium nitrate, that is 1,000 parts in all, to form a homogeneous, pliable paste.

This paste may be printed onto fabrics made of natural or regenerated cellulose or of synthetic fibers of the most diverse types by means of rollers or screens in the usual manner. After drying at normal or elevated temperature and subsequent heat treatment for some minutes at 120-150" C. brown printing elfects have excellent rubbing, Washing and light fastness are obtained.

Example 8 A mixture consisting of 50 parts of the pigment dyestuff according to Example 1, l -parts 0f St'aybclite ester 10 (glycerine ester of hydrated colophonium), 200 parts of sodium chloride and 18 parts of diacetone alcohol are treated in a kneader under cooling until the desired degree of fineness of the pigment is obtained. The sodium chloride and the diacetone alcohol are then removed from the kneading mass by introducing water having a tem perature of 8 0 C. The kneading mass itself is preserved. The salt-free and solvent-free kneading product is completely dried by heating the kneader with steam and pulverised in the kneader after cooling.

The preparation may be used, for example, for coloring lacquers. To this end, the preparation is advantageou'sly mixed into a paste with a little toluene and the paste obtained is mixed together with the lacquer.

Example 9 150 parts of the dry brown pigment according to Example 1 are ground together with 300 parts of a casein solution of 20% strength, 40 parts of a dispersing agent and 250 parts of distilled water in a suitable apparatus until the major part of the pigment particles has a size of less than 1 The pigment paste obtained is mixed up with 50 parts of a wax emulsion of 30% strength and another 200 parts of a casein solution of 20% strength and in this way a homogeneous pigment paste of 15% strength is obtained. 50 parts of this pigment preparation of 15% strength are well mixed with 100 parts of a casein solution of 20% strength, parts of sodium sulforicinoleate, 50 parts of a egg albumin solution and 870 parts of distilled water.

This pigment dispersion, which is ready for use, is applied once or twice to pre-dyed chrome grain leather by means of a plush board or hairbrush. Then follows the levelling application with the same pigment solution by spraying on at a pressure of 4 to 5 atmospheres. Thereupon, a casein solution of 20% strength is applied in the same manner, briefly dried and hardened with a formaldehyde solution of 810% strength. By mechanical glazing and hydraulic pressing of the leather surface at 60- 80 C. and a pressure of 150-200 atmospheres, the pigment application is sealed off. The dye has good light fastness and excellent fastness to wet rubbing and high transparency.

Both during the glazing and during the hot pressing, no color change can be observed.

Doubling of the quantity of pigment used in the finish- 7 ing solution effects a deepening of the color without shifting the color shade.

The above described brown pigment paste can be mixed with suitable similarly composed pigment preparations. In this Way, for example, in combination with white pigments brown even pastel tones having excellent light and migration fastness are obtained.

Example 10 For the so-called ironing preparation, binders based on polyacrylic acid ester inter alia may be employed without any trouble in addition to the brown pigment paste; in this way softer and more flexible covering layers are obtained than with the sole use of casein binders.

In order to produce an ironing preparation, the pigment solution may be composed as follows:

50 parts of a brown pigment paste of strength, 1 00 parts of casein solution of strength, parts of sodium sulforicinoleate, 150 parts of a 40% emulsion of a polyacrylic acid ester and 675 parts of distilled water. This thinly liquid pigment suspension is first applied to the generally bulfed leather to bedyed by means of a plush board. After drying and hydraulic pressing at 60 C. and a pressure of -150 atmospheres, the levelling application ismade with the same pigment solution by spraying on at a pressure of 4-5 atmospheres.

Finally, a glazing coat is applied to the dyed leather which consists of parts of a casein solution of 20% strength which is thereafter fixed by spraying over with a formaldehyde solution of '810% strength. After thorough drying, the leather surface is once more pressed hydraulically (75-80 C., 200 atmospheres pressure).

The dye is excellently fast to wet rubbing and is migration fast. In addition to the good light fastness, the high transparency, vividness and natural appearance are especially worth mentioning.

What is claimed is:

1. A member selected from the group consisting of cellulose, cellulose esters, casein, vinylpolymers, aminoplasts and alkyd resins having incorporated therein, in finely divided form, a dyestuff of the formula l I N 02 O R O R N 02 wherein R is a lower alkyl group.

2. A composition as defined in claim 1, wherein the dyestuif has an average particle diameter of at most 3,44.

3. An aminoplast resin having incorporated therein, in finely divided form, a dyestuff of the formula I R (g R I l 02 I l N 02 O R O R I l 02 wherein R is a lower alkyl group. 5. A melamine-formaldehyde resin having incorporated therein, in finely divided form, a dyestuif of the formula N02 0 R O R N03 wherein R is a lower alkyl group. 6. A viscose'spinning mass having incorporated there in, in finely divided form, a dyestufi of the formula N O z 0 R O R N 02 wherein R is a lower alkyl group.

7. A cellulose acetate spinning mass having incorporated therein, in finely divided form, a dyestuif of the formula WN-QNHQQ-NHQNO:

N02 R on N02 wherein R is a lower alkyl group.

8. Casein having incorporated therein, in finely divided form, a dyestutf of the formula N O n O R O R N O 2 wherein R is a lower alkyl group.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS Klinkenstein et a1 Mar. 9, 1943 Olpin et a1. Jan. 29, 1946 Vesce Aug. 18, 1953 Merian Mar. 24, 1959 Locher et a1. Apr. 28, 1959 Armento et a1. Nov. 3, 1959 870121. (June 25, 1957).

Lubs: Chemistry of Synthetic Dyes and Pigments, Monograph Series, No. 127 (1955), pages 49 and 196. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF CELLULOSE, CELLULOSE ESTERS, CASEIN, VINYLPOLYMERS, AMINOPLASTS AND ALKYD RESINS HAVING INCORPORATED THEREIN, IN FINELY DIVIDED FORM, A DYESTUFF OF THE FORMULA 